CN103880064A - Method for in-situ growth of two-dimensional lamellar structured nano-zinc oxide on ceramic tube - Google Patents
Method for in-situ growth of two-dimensional lamellar structured nano-zinc oxide on ceramic tube Download PDFInfo
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Abstract
The invention relates to a method for in-situ growth of two-dimensional lamellar structured nano-zinc oxide on a ceramic tube, and belongs to the technical field of preparation of nano sensors. The method comprises the following steps: preparing a zinc oxide seed crystal layer on an aluminum oxide ceramic tube taken as a substrate by utilizing an impregnation method; and growing a mixed solution of zinc nitrate and hexamethylene tetramine on the aluminum oxide ceramic tube containing the zinc oxide seed crystal layer by utilizing a hydrothermal method so as to obtain zinc oxide nanosheets. According to the method, the two-dimensional lamellar structured nano-zinc oxide is grown in an aqueous solution at a high temperature and under a high pressure; and convection flows of the solution are generated by controlling the temperature difference of the solution in a high-pressure autoclave so as to form a hypersaturated state, thereby growing a lamellar crystal. The two-dimensional lamellar structured nano-zinc oxide grown on the aluminum oxide ceramic tube is controllable in shape, wherein the nanosheets are of a wurzite hexagonal structure and are uniform in size, namely, each of nanosheets is about 1 to 2 microns in size; and the nanosheets are mutually connected to form a network. In addition, the response of the nano-zinc oxide to the ethyl alcohol can reach 40; and the nano-zinc oxide has the good selectivity to the ethyl alcohol.
Description
Technical field
The present invention relates to a kind of on vitrified pipe the method for growth in situ two-dimensional sheet structure nano zinc oxide, belong to the preparing technical field of nano-sensor.
Background technology
Along with science and technology and industrial progress, the toxic and harmfuls such as various industrial gaseous wastees, vehicle exhaust have all caused serious harm to atmospheric environment and resident healthy, therefore, for detection of the gas sensor of toxic and harmful, the effect in the people's productive life is increasing.Gas sensor, in the widespread use of the aspects such as environmental monitoring, automatic control, becomes the message elements of industrial and agricultural production and national defense construction widespread demand.
ZnO is N-shaped Semiconductor gas sensors material, aspect gas sensor, receives much concern.ZnO is as a kind of important II-VI family direct band gap semiconductor material with wide forbidden band, can grow multiple nanostructure, as nano wire, nano belt, nanometer wall, nanotube etc., the variation of pattern can cause the difference of some physical properties, plays an important role for the performance that improves related device.In the process of ZnO Materials, its pattern is mainly zero-dimension structural if nano particle, one-dimentional structure are if nano wire and three-dimensional structure are as ball-like structure etc.2007, the people such as other sharp sword have utilized immersion method growth in situ on alumina ceramic tube ZnO nano-wire, the ZnO nano-wire of described preparation is grown directly upon on vitrified pipe, in the time preparing sensor, without ZnO nano-wire being coated on vitrified pipe, this is simplified the preparation technology of gas sensor again.But due to contact difficulty between vertical nano wire, carrier transport difficulty, makes gas sensor resistance larger, shows as sensitivity lower.
Than a peacekeeping three-dimensional structure, the sheet structure of two dimension shows improves the not available advantage of a peacekeeping three-dimensional structure, as advantages such as high-specific surface area, difficult reunions.So, if vertical-growth in vitrified pipe be nanometer sheet, likely can overcome the shortcoming of " between vertical nano wire contact difficulty, carrier transport difficulty, makes gas sensor resistance larger, shows as sensitivity lower ".Therefore, the focus of research is how to obtain vertical-growth in the nanometer sheet of vitrified pipe at present.But, in prior art, do not introduce about " vertical-growth is in the method for the nanometer sheet of vitrified pipe " is relevant.
Summary of the invention
Experimental studies have found that, adopt immersion method (method of growth in situ ZnO nano-wire), adjust the parameters such as temperature of reaction, time, material concentration and only can obtain the nano wire that grows in vitrified pipe or the nanotube that form is different, but cannot be on vitrified pipe growth in situ two-dimensional sheet structure nano zinc oxide.As can be seen here, nanostructure process of growth on alumina ceramic tube is restricted by multiple factors, and those skilled in the art cannot directly obtain according to the method for growth in situ ZnO nano-wire the method for growth in situ two-dimensional sheet structure nano zinc oxide on vitrified pipe.
One of goal of the invention of the present invention: provide a kind of on vitrified pipe the method for growth in situ two-dimensional sheet structure nano zinc oxide.
And the present invention is taking alumina ceramic tube as substrate, utilize pickling process on alumina ceramic tube substrate, to prepare zinc oxide inculating crystal layer, then utilize hydrothermal method to make the mixing solutions of zinc nitrate and hexamethylenetetramine grow into Zinc oxide nano sheet on the alumina ceramic tube that contains zinc oxide inculating crystal layer.The present invention adopts hydrothermal method, and two-dimensional sheet structure nano zinc oxide is in High Temperature High Pressure
the aqueous solutionmiddle growth forms; Different from the growing environment of immersion method ZnO nano-wire.In High Temperature High Pressure
the aqueous solutionunder growing environment, those materials insoluble or indissoluble under atmospheric condition can dissolve, and maybe can react generation and can dissolve the product of this material; In addition, make to produce by controlling the temperature difference of solution in autoclave
convection currentgrow crystal to form hypersaturated state.So, of the present invention on vitrified pipe the growth mechanism of growth in situ two-dimensional sheet structure nano zinc oxide completely different from the growth mechanism of growth in situ ZnO nano-wire.
In addition, adopt in the process of the method growth in situ two-dimensional sheet structure nano zinc oxide on vitrified pipe, the mol ratio of concentration, zinc nitrate and the hexamethylenetetramine of the mixing solutions of structure and morphology, zinc nitrate and the hexamethylenetetramine of zinc oxide inculating crystal layer, hydrothermal growth temperature, the hydrothermal growth time all can be on the structure generation remarkably influenced of nano zine oxide; Wherein any one factor is slightly controlled improperly, cannot obtain two-dimensional sheet structure.Therefore, the present invention has carried out strict restriction to above-mentioned processing parameter.
So, provided by the invention on vitrified pipe the method for growth in situ two-dimensional sheet structure nano zinc oxide, the steps include:
(1) configuration zinc oxide inculating crystal layer solution:
Two water zinc acetates and thanomin are dissolved in to ethylene glycol monomethyl ether;
Or, by two water zinc acetate dissolve with ethanol, then adding lithium hydroxide, sonic oscillation is extremely
Lithium hydroxide complete reaction;
Wherein, the mass ratio of two water zinc acetates and thanomin is 4.4:1.2; Two water zinc acetate and hydrogen
The mass ratio of Lithium Oxide 98min is 2.7:0.74;
(2) growth of two-dimensional sheet structure nano zinc oxide:
After alumina ceramic tube is flooded in zinc oxide inculating crystal layer solution, in 350 DEG C of calcining 30 min; Then, be placed in the zinc nitrate of 0.025 mol/l and the mixing solutions autoclave of hexamethylenetetramine are housed, in 95 DEG C of incubation water heating growth 3-12h, must grow in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube;
Wherein, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1.
Aforesaid method, in step (), ethylene glycol monomethyl ether and ethanol use as solvent, and those skilled in the art can determine its consumption according to common practise; In step (two), the equipment that hydro-thermal reaction is used, those skilled in the art can determine according to common practise.In the present invention, the consumption of ethylene glycol monomethyl ether is 25ml/4.4g bis-water zinc acetates; The consumption of ethanol is 250ml/5.4g bis-water zinc acetates; The described liner for autoclave is tetrafluoroethylene, and volume is 50 ml.
Aforesaid method, in step (), zinc oxide inculating crystal layer solution can exert an influence to the formation of zinc oxide inculating crystal layer; In order to obtain the good zinc oxide inculating crystal layer of form on alumina ceramic tube, after two water zinc acetates and thanomin are dissolved in to ethylene glycol monomethyl ether, preferred, leave standstill 12h;
Or the sonic oscillation time is 1h.
Aforesaid method, in step (two), the hydrothermal growth time, while being 3h, the nanometer sheet obtaining was very rare; So the preferred hydrothermal growth time is 6-12h.And the two-dimensional sheet structure obtaining during for 8h when the hydrothermal growth time is ideal; So the highly preferred hydrothermal growth time is 8h.
Aforesaid method, in step (two), in order to obtain the good zinc oxide inculating crystal layer of form on alumina ceramic tube, alumina ceramic tube was used acetone, ultrasonic 20 min of the ultrasonic difference of ethanol before using.
Two of object of the present invention, provides a kind of air-sensitive alumina ceramic tube that adopts above-mentioned preparation method to obtain.Wherein, the size of alumina ceramic tube, can determine according to concrete need of production.Wherein a kind of air-sensitive alumina ceramic tube provided by the invention, alumina-ceramic length of tube used is 4 mm, internal diameter 1 mm, external diameter 1.4 mm.
Three of object of the present invention, provides a kind of gas sensor that adopts above-mentioned air-sensitive alumina ceramic tube to prepare.Gas sensor of the present invention can be widely used in posting the detection of gas, comprises ethanol, Virahol, the organic gass such as acetone.Wherein a kind of gas sensor provided by the invention, its integrated gold electrode in air-sensitive ceramic oxide pipe two ends, between gold electrode at a distance of 2 mm, integrated four platinum wires on gold electrode.
Four of object of the present invention, provides a kind of gas sensor of nickel oxide/Zinc oxide nano sheet heterojunction, is to utilize pulsed laser deposition technique, on the air-sensitive alumina-ceramic tube-surface providing, deposits p-type semiconductor material nickel oxide in goal of the invention two.
Beneficial effect
The method of growth in situ two-dimensional sheet structure nano zinc oxide on vitrified pipe is disclosed first;
Method of the present invention, without being first prepared into the nano wire that grows in alumina ceramic tube, but direct growth is two-dimensional sheet structure; Step is simple, consuming time short;
Zinc oxide nano sheet of the present invention be grown directly upon on alumina ceramic tube, without coating; The preparation process of two-dimensional sheet structure nano zinc oxide is also the preparation process of air-sensitive vitrified pipe; Simplify preparation technology's (gas sensitive also needs to be coated in vitrified pipe after having prepared) of traditional gas sensor, time saving and energy saving, cost-saving;
The two-dimensional sheet structure nano zinc oxide pattern of prepared by the present invention grow in alumina ceramic tube is controlled, nanometer sheet well-crystallized, for hexagonal wurtzite structure, size uniform, be about 1-2 μ m, be interconnected with one another formation network; Can reach 40 to the response of ethanol, and ethanol is shown to good selectivity;
Nickel oxide/Zinc oxide nano sheet heterojunction sensor of the present invention, can significantly improve the air-sensitive performance of Zinc oxide nano sheet; Triethylamine is shown to good selectivity, and there is larger response.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope picture of the Zinc oxide nano sheet sensor sensing material part prepared of embodiment 1;
Fig. 2 is the X ray diffracting spectrum of the Zinc oxide nano sheet prepared of embodiment 1;
Fig. 3 is the air-sensitive performance collection of illustrative plates of the Zinc oxide nano sheet gas sensor prepared of embodiment 1;
Fig. 4 is nickel oxide/ZnO heterojunction nanometer sheet scanning electron microscope picture (a) and EDS energy dispersion spectrogram (b) prepared by the present invention;
Fig. 5 is the air-sensitive performance figure of nickel oxide/Zinc oxide nano sheet heterojunction gas sensor of preparing of the present invention;
Fig. 6 is the field emission scanning electron microscope picture of the nano zinc oxide material sensor sensing material part prepared of comparative example 1;
Fig. 7 is the field emission scanning electron microscope picture of the nano zinc oxide material sensor sensing material part prepared of comparative example 3.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry for standby.4.4g bis-water zinc acetates are added in 25 ml ethylene glycol monomethyl ether; In the dissolution process of two water zinc acetates, 1.2g thanomin is added drop-wise in above-mentioned solution; After two water zinc acetates and thanomin dissolve completely, obtain zinc oxide inculating crystal layer solution; Leave standstill 12h for subsequent use.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, being placed in liner is that tetrafluoroethylene, volume are the autoclave of 50 ml, for subsequent use.The alumina ceramic tube cleaning up is immersed in to 4-12 hour in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, alumina-ceramic tube-surface forms one deck zinc oxide inculating crystal layer.To put into autoclave with the alumina ceramic tube of zinc oxide inculating crystal layer, in 95 DEG C of incubation water heating growth 8h, obtain growth in situ in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube.The scanning electron microscope of this two-dimensional sheet structure nano zinc oxide as shown in Figure 1; Can find out from Fig. 1, ZnO nano chip size is comparatively even, is about 1-2 μ m, is interconnected with one another formation network.The X ray diffracting spectrum of this two-dimensional sheet structure nano zinc oxide as shown in Figure 2; As can be seen from Figure 2, nanometer sheet well-crystallized, is hexagonal wurtzite structure, there is no other impurity.Be welded into gas sensor and tested its air-sensitive performance, as shown in Figure 3.As can be seen from Figure 3, under optimal working temp, ZnO nano sheet can reach 40 to the response of ethanol, and ethanol is shown to good selectivity.
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry
Dry for subsequent use.Take 2.7g zinc acetate and join in 125 mL ethanol, reflux in 95 DEG C of waters bath with thermostatic control, after zinc acetate dissolves completely, continues heating 1 h, is then cooled to room temperature.Add again 0.74 g lithium hydroxide, sonic oscillation 1h; Obtain uniform zinc oxide inculating crystal layer solution.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, being placed in liner is that tetrafluoroethylene, volume are the autoclave of 50 ml, for subsequent use.The alumina ceramic tube cleaning up is immersed in to 4-12 h in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, change aluminium vitrified pipe surface and form one deck zinc oxide inculating crystal layer.To put into autoclave with the alumina ceramic tube of zinc oxide inculating crystal layer, in 95 DEG C of incubation water heating growth 8h, obtain growth in situ in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube.The scanning electron microscope of this two-dimensional sheet structure nano zinc oxide as shown in Figure 1.Prepared two-dimensional sheet structure nano zinc oxide and p-type semiconductor material nickel oxide are carried out to heterojunction.Utilize pulsed laser deposition technique at two-dimensional sheet structure nano zinc oxide surface deposition p-type semiconductor material nickel oxide, construct heterojunction sensor, its scanning electron microscope and energy spectrogram are as shown in Figure 4.After depositing nickel oxide as can be seen from Figure 4, nanometer sheet surface presents grey, from finding out there is the existence at nickel peak spectrogram, nickel oxide has been described on nanometer sheet surface deposition.It is directly made to gas sensor.Its performance map is as shown in Fig. 5.Fig. 5 is the selectivity collection of illustrative plates of nickel oxide/Zinc oxide nano sheet heterojunction sensor to gas with various, and as can be seen from the figure, after constructing heterojunction, this material shows good selectivity to triethylamine, and has larger response.
Embodiment 3
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry for standby.4.4g bis-water zinc acetates are added in 25 ml ethylene glycol monomethyl ether; In the dissolution process of two water zinc acetates, 1.2g thanomin is added drop-wise in above-mentioned solution; After two water zinc acetates and thanomin dissolve completely, obtain zinc oxide inculating crystal layer solution; Leave standstill 12h for subsequent use.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, being placed in liner is that tetrafluoroethylene, volume are the autoclave of 50 ml, for subsequent use.The alumina ceramic tube cleaning up is immersed in to 4-12 h in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, change aluminium vitrified pipe surface and form one deck zinc oxide inculating crystal layer.To put into autoclave with the alumina ceramic tube of zinc oxide inculating crystal layer, in 95 DEG C of incubation water heatings, 3 h that grow, obtain growth in situ in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube.The X ray diffracting spectrum of this two-dimensional sheet structure nano zinc oxide is consistent with embodiment's 1; Its scanning electron microscope (SEM) photograph and air-sensitive performance map sheet and embodiment's 1 is approximate.
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry for standby.4.4g bis-water zinc acetates are added in 25 ml ethylene glycol monomethyl ether; In the dissolution process of two water zinc acetates, 1.2g thanomin is added drop-wise in above-mentioned solution; After two water zinc acetates and thanomin dissolve completely, obtain zinc oxide inculating crystal layer solution; Leave standstill 12h for subsequent use.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, being placed in liner is that tetrafluoroethylene, volume are the autoclave of 50 ml, for subsequent use.The alumina ceramic tube cleaning up is immersed in to 4-12 h in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, change aluminium vitrified pipe surface and form one deck zinc oxide inculating crystal layer.To put into autoclave with the alumina ceramic tube of zinc oxide inculating crystal layer, in 95 DEG C of incubation water heating growth 12h, obtain growth in situ in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube.The X ray diffracting spectrum of this two-dimensional sheet structure nano zinc oxide is consistent with embodiment's 1; Its scanning electron microscope (SEM) photograph and air-sensitive performance map sheet and embodiment's 1 is approximate.
Comparative example 1
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry for standby.Take 2.7g zinc acetate and join in 125 mL ethanol, reflux in 95 DEG C of waters bath with thermostatic control, after zinc acetate dissolves completely, continues heating 1 h, is then cooled to room temperature.Add again 0.74 g lithium hydroxide, sonic oscillation 1h; Obtain uniform zinc oxide inculating crystal layer solution.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, be placed in the beaker that volume is 50 ml, for subsequent use with preservative film capping.The alumina ceramic tube cleaning up is immersed in to 4-12 hour in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, alumina-ceramic tube-surface forms one deck zinc oxide inculating crystal layer.To put into growth media with the alumina ceramic tube of zinc oxide inculating crystal layer, in 90 DEG C of water bath with thermostatic control growth 3h, obtain growth in situ in the nano zine oxide of alumina ceramic tube, its field emission scanning electron microscope picture as shown in Figure 6.
Comparative example 2
By ultrasonic effective the alumina-ceramic of trying to win sb.'s favor in advance acetone 20 min to clean up, and dry for standby.4.4g bis-water zinc acetates are added in 25 ml ethylene glycol monomethyl ether; In the dissolution process of two water zinc acetates, 1.2g thanomin is added drop-wise in above-mentioned solution; After two water zinc acetates and thanomin dissolve completely, obtain zinc oxide inculating crystal layer solution; Leave standstill 12h for subsequent use.Get zinc nitrate and hexamethylenetetramine according to the mol ratio of 1:1, add water and be mixed with the growth media of 0.025 mol/l, be placed in the beaker that volume is 50 ml, for subsequent use with preservative film capping.The alumina ceramic tube cleaning up is immersed in to 4-12 hour in zinc oxide inculating crystal layer solution, then takes out, in 350 DEG C of annealing calcining 30 min; Now, alumina-ceramic tube-surface forms one deck zinc oxide inculating crystal layer.To put into growth media with the alumina ceramic tube of zinc oxide inculating crystal layer, in 95 DEG C of water bath with thermostatic control growth 3h, obtain growth in situ in the nano zine oxide of alumina ceramic tube, its field emission scanning electron microscope picture and Fig. 6 are approximate.
Comparative example 3-11
Adopt the method steps of embodiment 1, adopt the parameter in following table:
| ? | Parameter A | B parameter | Parameters C | Parameter D | Parameter E |
| Comparative example 3 | 4.4:1 | 2.7：0.74 | 1:1 | 350℃ | 95℃ |
| Comparative example 4 | 4.5:1.2 | 2.7：0.74 | 1:1 | 350℃ | 95℃ |
| Comparative example 5 | 4.4:1.2 | 2.7：0.8 | 1:1 | 350℃ | 95℃ |
| Comparative example 6 | 4.4:1.2 | 2.8：0.74 | 1:1 | 350℃ | 95℃ |
| Comparative example 7 | 4.4:1.2 | 2.7：0.74 | 1:1.1 | 350℃ | 95℃ |
| Comparative example 8 | 4.4:1.2 | 2.7：0.74 | 1:0.9 | 350℃ | 95℃ |
| Comparative example 9 | 4.4:1.2 | 2.7：0.74 | 1.1:1 | 350℃ | 95℃ |
| Comparative example 10 | 4.4:1.2 | 2.7：0.74 | 1:1 | 345℃ | 95℃ |
| Comparative example 11 | 4.4:1.2 | 2.7：0.74 | 1:1 | 350℃ | 92℃ |
In table, parameter A: the mass ratio of two water zinc acetates and thanomin;
B parameter: the mass ratio of two water zinc acetates and lithium hydroxide;
Parameters C: the mol ratio of zinc nitrate and hexamethylenetetramine:
Parameter D: calcining temperature; Parameter E: hydrothermal temperature;
The prepared growth in situ of comparative example 3 in the field emission scanning electron microscope picture of the nano zine oxide of alumina ceramic tube as shown in Figure 7; The prepared growth in situ of comparative example 4-10 is all similar to Fig. 7 in the field emission scanning electron microscope picture of the nano zine oxide of alumina ceramic tube.
Claims (8)
1. a method for growth in situ two-dimensional sheet structure nano zinc oxide on vitrified pipe, is characterized in that, step is:
(1) configuration zinc oxide inculating crystal layer solution:
Two water zinc acetates and thanomin are dissolved in to ethylene glycol monomethyl ether;
Or, by two water zinc acetate dissolve with ethanol, then adding lithium hydroxide, sonic oscillation is extremely
Lithium hydroxide complete reaction;
Wherein, the mass ratio of two water zinc acetates and thanomin is 4.4:1.2; Two water zinc acetate and hydrogen
The mass ratio of Lithium Oxide 98min is 2.7:0.74;
(2) growth of two-dimensional sheet structure nano zinc oxide:
After alumina ceramic tube is flooded in zinc oxide inculating crystal layer solution, in 350 DEG C of calcining 30 min; Then, be placed in the zinc nitrate of 0.025 mol/l and the mixing solutions autoclave of hexamethylenetetramine are housed, in 95 DEG C of incubation water heating growth 3-12h, must grow in the two-dimensional sheet structure nano zinc oxide of alumina ceramic tube;
Wherein, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1.
2. method according to claim 1, is characterized in that, the consumption of ethylene glycol monomethyl ether is 25ml/4.4g bis-water zinc acetates; The consumption of ethanol is 250ml/5.4g bis-water zinc acetates; The described liner for autoclave is tetrafluoroethylene, and volume is 50 ml.
3. method according to claim 1, is characterized in that, in step (), after two water zinc acetates and thanomin are dissolved in ethylene glycol monomethyl ether, leaves standstill 12h;
Or adding the sonic oscillation time after lithium hydroxide is 1h.
4. method according to claim 1, is characterized in that, in step (two), the hydrothermal growth time is 6-12h.
5. method according to claim 4, is characterized in that, in step (two), the hydrothermal growth time is 8h.
6. one kind adopts the air-sensitive alumina ceramic tube that in claim 1～5 prepared by the method described in any one.
7. a gas sensor that adopts air-sensitive alumina ceramic tube claimed in claim 6 to prepare.
8. a gas sensor for nickel oxide/Zinc oxide nano sheet heterojunction, is characterized in that, utilizes pulsed laser deposition technique, on air-sensitive alumina-ceramic tube-surface claimed in claim 6, deposits p-type semiconductor material nickel oxide.
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